The One-electron Reduction of Carbonium Ions. VIII. The Reducibility of Hetero-substituted Tropylium Ions as Measured by the Competitive Reduction Method with Zinc Powder
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概要
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A series of hetero-substituted tropylium salts (X-C<SUB>7</SUB>H<SUB>6</SUB><SUP>+</SUP>·Y<SUP>−</SUP>), including three new compounds, have been synthesized. Their relative reactivities in one-electron reductions with zinc powder have been determined by the use of a competitive-reaction method, which gave the following reactivity sequence: CH<SUB>3</SUB>O-C<SUB>7</SUB>H<SUB>6</SUB><SUP>+</SUP> (<I>k</I><SUB>rel.</SUB>=0.0295), <I>t</I>-C<SUB>4</SUB>H<SUB>9</SUB>-C<SUB>7</SUB>H<SUB>6</SUB><SUP>+</SUP> (0.146), CH<SUB>3</SUB>S-C<SUB>7</SUB>H<SUB>6</SUB><SUP>+</SUP> (0.255), C<SUB>7</SUB>H<SUB>7</SUB><SUP>+</SUP> (1.00), C<SUB>6</SUB>H<SUB>5</SUB>-C<SUB>7</SUB>H<SUB>6</SUB><SUP>+</SUP> (2.50), (C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB>Si-C<SUB>7</SUB>H<SUB>6</SUB><SUP>+</SUP> (7.50), Cl-C<SUB>7</SUB>H<SUB>6</SUB><SUP>+</SUP> (16.8), CH<SUB>3</SUB>OCO-C<SUB>7</SUB>H<SUB>6</SUB><SUP>+</SUP> (35.7), NC-C<SUB>7</SUB>H<SUB>6</SUB><SUP>+</SUP> (163). The values of log<I>k</I><SUB>rel.</SUB> for the <I>t</I>-C<SUB>4</SUB>H<SUB>9<SUP>−</SUP></SUB>, H-, and C<SUB>6</SUB>H<SUB>5</SUB>-C<SUB>7</SUB>H<SUB>6</SUB><SUP>+</SUP> ions exhibit a good linear relationship with those of log<I>k</I><SUB>2</SUB> in the chromous-ion reduction. A linear correlation is also observed between log<I>k</I><SUB>rel.</SUB> and the transition energy for the charge-transfer band of the respective cations, with pyrene as a donor. A plot of log<I>k</I><SUB>rel.</SUB> against σ<I><SUB>p</SUB></I> (for the ring substituent, X) gives a greater ρ-value (+4.0) than in the case of X-C<SUB>6</SUB>H<SUB>4</SUB>-C<SUB>7</SUB>H<SUB>6</SUB><SUP>+</SUP> (+1.31), reflecting the influence of the direct substitution on the tropylium ring.
- 公益社団法人 日本化学会の論文
著者
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Komatsu Koichi
Department Of Environmental And Biological Chemistry Fukui University Of Technology
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Sakaguchi Osamu
Department Of Chemistry Graduate School Of Science And Technology Kumamoto University
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Okamoto Kunio
Department of Fuel Chemistry Faculty of Engineering Kyoto University
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Sakaguchi Osamu
Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University
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